CZ319496A3 - Mixture for producing shaped corpuscles from fibrous webs - Google Patents

Abstract

PCT No. PCT/EP95/01643 Sec. 371 Date Jan. 28, 1997 Sec. 102(e) Date Jan. 28, 1997 PCT Filed Apr. 29, 1995 PCT Pub. No. WO95/30034 PCT Pub. Date Nov. 9, 1995A mixture for producing moulded articles from fibre mats containing a) 20 to 45 wt. % of a powdered binder mixture, b) 80 to 55 w. % of organic and/or inorganic fibres, characterised in that the powdered binder mixture contains a1) 30 to 90 wt. % of phenol resin and a2) 70 to 10 wt. % of powder coating waste and moulded articles produced therefrom.

Description

Technical field

The invention relates to a special composition for the production of fibrous webs and to a process for the production thereof. Preferred are products made from fibrous webs and binders.

BACKGROUND OF THE INVENTION Fiberglass-based shaped bodies are widely used in industry. these are nonwoven fibers of various kinds which can be mixed with the binder. Pre-products, so-called prepregs, can then be produced from these fibrous webs, which are then formed by the corresponding processing tools, cured and optionally adjusted. The tower can be made directly from the fibers and powder of the corresponding endless fiber web. lato. shaped bodies not; o Plates are widely used. In the automotive industry, these products are used, for example, as molded bodies, for example, as insulating materials for engine covers, rails, or for insulating the space for luggage binders. Another field of application is damping for doll goods (boards), for example, as insulating material in washing machines, clothes dryers or loudspeakers, in sound absorbing walls. they may be provided with other coatings, for example by serrating, laminating or laminating

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The optically stable heat sinks are then driven by the sides of the door, the lining of the ceiling into or planar parts provided with such a decorative coating, for example as a cover pocket or as an automotive industry.

The processes for producing fiber webs or for mixing these webs with binder powder are known. In this case, the fibrous material is homogenized, for example, in a fiber mixing chamber, and is folded onto the conveyor belt as a loose layer of fibers.

The jersey binder is then applied to the fibrous material, for example by means of metering rollers or vibrating troughs. Then, the fiber / binder mixture is swirled and mixed homogeneously in a closed system by means of an air stream. The homogeneous mixture of fibers and binder powder is processed into an endless web. The ingredients of this mixture may be agglomerated with either gentle heating followed by cooling of the preforms arise where _t / prepregs / or preparing a planar disc or goods which are already fully cured. frepregs are not yet fully cured, but they are stable when stored, processed to the final form:

The temperature will be thermally at a temperature of up to. to 21 ° C, whereby three-dimensional duroplastic shaped bodies are obtained. - '.

The requirements for these shaped bodies with respect to surface texture, and color are variable, but at elevated temperature or load

-3dlouhodobým storage must be guaranteed to get you ^T mechanical stability. However, it is necessary to use a binder which binds the fibrous web together well in order to produce a stable molding and curing after relatively long molding. The binders currently used are relatively expensive. Moreover, phenolic resins threaten zoravi. The industry is heavily involved in reducing costs. Especially in the case of the above-described moldings, such as insulating materials for engine housings, rails or insulating materials, alternatives to expensive, technically pure resins are being sought. SUMMARY OF THE INVENTION

It is an object of the present invention to provide a binder composition for the production of fibrous web shaped bodies in which a large proportion of the commonly used pure resins have been replaced by other substances which nevertheless result in stable stability. reactive, mixtures roj- ¹ ' »which are suitable for producing fiber prepro GSZ .rouna vytvrzeuého goods or the fiber web. Another task is to reduce the proportion of substances harmful to health. These binder mixtures must meet the usual requirements for the production of fibrous web-shaped bodies while providing hardened, stable shaped bodies which can be adapted for various applications. · '''It turned out that -This ·. "Object can be achieved using powder coating waste _t, as a binder or binders for producing molded bodies from the VLA-4kenného web. Surprisingly, it has been found that the resins which are commonly used can be replaced by at least a considerable proportion of the powdered waste wastes.

The subject of the invention is a composition for the production of molded bodies from fiber. % and / or from about 20 to about 45 rt by weight; Powdered, binder mixtures of 30 to 55 rt wt. -organických and / Neto inorganic fibers, which are characterized 'in that the binder comprises a powder mixture &] / 30 to $ 0 rt hmot.fenolové resin a. _;; (70 to 10) wt. powder coating waste.

It is a further object of the present invention to use powder coating wastes for the manufacture of shaped bodies comprising a fibrous web.

Another object is the use of these lacquer wastes to bind fibrous webs.

Powders have been increasingly used in the medical industry. These have the advantage that dají'nanášet manner-without solvent-sulfadoxime can considerably reduce emissions burdensome for the environment - a centering method HFF _r .nanášení- powder .laků-bears the disadvantage that a considerable part of the powder get on movlékaný; These powders are collected in a paint booth as a so-called spray. Iraqis are susceptible to germany size and purity; ^x roto se -spray must be disposed of as waste? Even in the last stage of the production of the lacquer powder, the powder extrudates of the lacquer powder are ground. Fine dust escapes in this process, which has a disruptive effect on the coating process. Therefore, this dust is removed as much as possible. The dust can be "5" OTf "reaper" again z'pr ac network and t ~ 'ousia ^-' or PR-o- -ods Tr --------- nova as special waste.

I ^T fibers used for a variety of fibrous webs is: woven, felted or mixed fibers. The fibers consist of known materials, for example natural, organic and inorganic fibers. Examples thereof are glass fibers, mineral wool fibers, polyester fibers, acrylic resin fibers, polyolefin fibers, wool fibers, cotton fibers, flax fibers, or the like. Advantageous. are textile fibers, in particular cotton fibers, for example, fibers of textile industry ε. - as well as fibers; A variety of fiber webs are known in the industry, and are known in the art. This can be done, for example, by carboxylation or by confusion. emerging fibrous. fleece. They may be substantially dry or optionally impregnated with additives.

The phenolic resins useful in the compositions of the present invention are conventional reactive phenolic resins which have long been known in the industry, for example, non-crosslinked phenolic resins. they are reactive and contain OH groups. Such resin does it? p'oú ~ employed for the production of molded .tělísek of vlákenhých'ro'in. '·' ř.apříklad may be-used 'phenolic resins based on phenol formaldehyde and ^one that is. known as resols or novolaks.

As a foot crosslinker, the washed resins may contain formaldehyde condensation products.

these resins are already extensively described in the literature, for example in ϋ.ΐ \. Shreve, The Chemical Process Industries, Chapt. Plastics, 1945 and available for sale. Other phenolic resins are also described in D2-A-33 33 656, hl-A-0 369 539 as in 1Ξ-Α-0 376 '432. Particularly preferred are phenolic resins of the novolak type.

The inactivity of phenolic resins is determined by the type and amount of crosslinking agent used. Generally, a sulfurization reaction occurs between 12 ° C to 222 ° C.

Worms generally exist in powder form. Suitable grain sizes are, for example, between 0.1 to 100.

_Of 500 microns, preferably between 2-1? Μιζ C, most preferably between 10 and 60 / um.

For example, in the grain size of the powder coating waste used, they are in the same range as the resins, and are preferably between 1 and 300 µm, most preferably between 1 and 60 µm. If powder coating wastes whose grain size is too small for the desired purpose are used, larger grain sizes can be obtained by sintering the particles.

The lacquer wastes to be used according to the invention are wastes of the known powder coatings. The powder coatings may, for example, be an ointment of epoxy resins, polyester resins, polyurethane resins or acrvlate resins, such as powder coatings.

- wastes falling off, for example, from spray booths or from defective batches in powder paint production. It is also possible to collect and use filter dusts ^- 7šíějně ^- so ljako ~ ^- ----- residues of grinding powder.

The powder coating wastes usable in the sachet of the present invention are not yet crosslinked. They contain reactive columns such as, for example, carboxyl groups, epoxy groups, hydroxyl groups, amino columns, amines to groups or isocyanate derivatives. They can react together during heating, crosslinking. depends on the underlying skeleton. Usually, between 120 and 22O 'O °, Powder lacquers · s · teplota-; · ¹ mi crosslinking re mi sáhuj ICI 150 ° C are preferably used in only small amounts, so that even at curing temperatures T-shaped šlísek about 0 DEG-Loo and _(achieve the fullest possible crosslinking used sm ^C "binders Additionally, they also that, in. high temperature curing. · especially · při.pouši- .. three fiber fleece of plastic fibers is the risk that the fibers are degraded, leading to a reduc tions., the stability of the shaped body. "It is preferred that - the crosslinking temperature powder coating are lower .lbO nes ^U Q and used powder coatings are known to the binder system. Here, the These are conventional resins, for example based on epoxy, polyester, polyethane or acrylate, epoxy powder coatings containing epoxy resins as the main binder component.

The dss sieves often use a hardener containing hydroxyl groups, and in particular amide or amine groups.

Furthermore, polyester powder coatings are known in which carboxyl-containing polyesters are the main constituent. Crosslinkers containing epoxy groups or amino-containing or amido-containing crosslinkers are known as crosslinkers. The existing crosslinkers have a higher functionality than the main binder component. when a powder of an epoxy-polyester mixture, so-called hybrid systems, is used, approximately the same proportions of polyesters or epoxy resins are present.

Polyurethane powder coatings are based on hydroxyl-containing polyesters which are protected by reversibly blocked polyisocyanates, for example by known preservatives, such as carp or ketzxime, and are wet. crosslinked or may be present as urethdione.

acrylic lacquer varnishes. are generally mixtures of two or more acrylate resins containing functional groups such as epoxy groups, carboxyl groups, hydroxyl groups or isocyanate groups. Again, the reactive groups are divided into different molecules.

Such powder binders are described, for example, in c.I. H .'-. Rris, ~ The Technology of Lowder Coats,

1976 or n.A. Bate, ~ ”The -Science of fowder doaé zmgs, ol. i, 1 ^ 90.

Colorless powder paints or powder paints with pigments can be used, in which case conventional inorganic or organic color pigments are possible as pigments in order to incorporate an effect pigment in the powder. , for example metallizing pigments, separation by color tone is not necessary. The fineness of the grain of the powder is not essential, it should only be ensured that a generally average sample of different powder residues is used to produce the binder mixture. This leads to better mixing behavior and more constant production of binder mixtures.

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Any individual powder coating can be used. In order to achieve the most consistent composition, the binder mixture and / or mixture are mixed. It is preferred that the present 'blend of epoxy, powders, and powders polyesterovýc I ¹ and ko «RR! this may optionally be replaced by up to 30% by weight of polyurethane powder and / or polyacrylate powder. ^x s FOM can .p- ímo- směs- and ^y ^ / ..and produce. so 'store in the range. ·. Another possible process is that the various components of the powder coating according to the chamic types described above are stored separately and only late before being further processed. - By hanging it with phenolic resins «Inside», these chemical types are mixed with different

The materials are mixed homogeneously, i.e., a sample is formed, which is mixed, which relates to the distribution of the composition according to the grain and pigmentation. Accordingly, the existing binders of the lacquer powders are dispensed with in the production of the binder powder and / or admixed with the quantities required.

Alternatively, other crosslinking agents may be incorporated into the mixtures.

The Gdpsdy powder coatings useful in the present invention are in the form of ground powder. In addition, a proportion is required; binders which are present in a coarser form are pre-ground to a suitable grain size. The binder may correspond to the order of magnitude given for the phenolic resin.

If desired, conventional additives or additives may be added to the powders; . For example, they may be catalysts, accelerators and fire retardants, and tin compounds such as dibutyltin dilaurate are preferably used as catalysts. carboxylic acid salts such as lithiunbenzoate, quaternary ammonium compounds such as tetrabutylammonium bromide, cetyltrimethylannonium bromide, benzylmethylammonium chloride, benzyltriethylammonium chloride or tetramethylammonium chloride or, for example, tertiary amines, or tertiary amines, such as tertiary amines, or tertiary amines. Suitable accelerators and crosslinkers are, for example, basic compounds containing epoxy groups, such as triglycidyl isocyanurates _: glycolurils, dicyandiamide or beta-hydroxylamides. furthermore, these additives can be added individually as powdered substances, as well as they can be introduced as a premix mixed with the proportion; ^- bonding, or may be p? 'Idávkovat-as a mixture with binder powder and /.

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In addition, flame retardants may be added. These are the customary known substances which are present in fire-protective coatings, the pros of which are thin, or tori-as-for-example-to-ice. loritar. sodium; phosphates such as ammonium phosphate or sodium phosphate; aluminum hydroxides or aluminum oxides; other suitable compounds are, for example, heavy metal containing compounds, such as tin oxide compounds or peroxybrominated or perchlorinated compounds such as tetrabromophenol. however, they preferably use flame retardants, free of heavy metals and free of halogen. These. The flame retardants are in the form of a powder, which can be introduced by means of a separate masterbatch, or can be dosed by means of a binder powder and / or can now be added as a co-mixture with the powder component. . The ligands are then introduced into the mixture with binders and / or. In general, however, it is preferable not to deposit any additional pigments, but only the fibrous fillers of the fibrous web or the pigments contained in the powder coatings and ₂ ). ·

.. 'further officially tem of the present invention, ^R Y moldings that can be produced by forming ·' and the partial or total curing of the above-described fiber mixture a'pojivá. If the fiber and binder mixtures are only partially cured, so-called nrepregs are obtained, which are then formed into the final mold by the next step of the rotting process.

to cure completely. If the mixture is to be fully cured, they are shaped by a customary c-shaped shape and at the appropriate cross-linking temperatures the existing binder mixture is cured.

The trepreg formed prior to curing a finished molding generally comprises 5 to 3% by weight. 20 to 45 wt. binder mixtures.

A preferred embodiment consists of a binder with 45 to 70 wt. % phenol resins and 30 to 55 wt. The above-described additives and additives may be present in an amount of up to 20%, preferably up to 15%. wherein the sum of the individual constituents ranges from 100 p. Any powder paint waste can be used. only one type of powder coating or a mixture of several types may be used, but a mixture of polyesters and epoxy resins is preferred. u is still. desirably, when the ratio of polyester powder to epoxy powder is 0.2: 1 to 7: 1, preferably 0.3: 1 to 1: 1. a sufficient number of reactive groups.

In order to manufacture the moldings according to the invention, the binder mixtures are homogenized and, together with possible additives, applied to the fibrous web. This is carried out in a manner known per se. The binder mixture is evenly distributed over the fibrous web and then a heating step can optionally be carried out. This results in particles intoxicating on the surface soften and firmly bonded to the fibrous web, even so-called prepregs are formed which will provide a storage-stable web and still be formable into a web. It must be ensured that the crosslinking is not yet complete, but that the binder can be further heat-formed, i.e. ae. .ta .-. z.esít.OV.at., __________________

The binder and / or prepregs as well as the cured moldings have a reduced proportion of free phenols or formaldehyde. This reduces the risk to these substances which are harmful to health. The moldings according to the invention can then be produced from the prepregs thus obtained. This is accomplished by known methods, such as forming and / or laminating, adjusting the prepregs. Once the prepregs have taken a suitable form, they are crosslinked using pressure and heat. it is carried out ^{at? t} -i temperatures of 140 to 200 ° U..Toba Jeans, crosslinking is at between TC and 5C0 sec, ie preferably less than 120 sec. This is chosen by the model used ť ~ 5.

phenolic resins; Is it done in kind? and curing the binder powder, thereby. The DC fibers are at least partially embedded and the resin is chemically crosslinked.

This results in a hardened duroplastic material. . Depending on the amount of material used and the press pressure used, the shaped bodies may contain cavities. The density of the shaped bodies can be between 50 and 1000 kg / m @ 2. This is dependent on the amount and type of fibers and the binder.

Such as good thermal insulation, shape stability up to 130 ° C, good sound insulation, good flexural strength, are not physiologically defective and control moisture, and can continue to do so.

process. - ·. .

if

AND

-14These shaped bodies may still be coated or serve as carriers of other building forces. This can happen, for example, by applying film together with the crosslinking and shaping. This is bonded firmly to the surface by means of a chemical reaction. Further, a special surface coating can be achieved by additional laminating and laminating the films. Methods of laminating molded bodies are widely used in the industry.

Furthermore, the surface of the shaped bodies can be flocked. in this case, short threads are fastened with adhesives. basically vertically to the surface, tat? then it creates a dense and soft surface. The methods of flocking are known; me. The shaped bodies produced from the spikes according to the invention can optionally be painted. In addition, all known coating compositions known in the industry can be used. This will produce smooth, glossy coatings.

The shaped bodies coated in this way have the desired decorative effect. Depending on the method chosen, soft, veined or even chemically resistant coated surfaces can be obtained. By additional use of flame retardants, fire-resistant moldings can be obtained.

The shaped bodies thus obtained can be used in various fields of industry. In particular, they can be used in the automotive industry, for example as parts for the interior trim of cars or sound or heat insulation. Other binder mixtures can be used as resins in clutch linings, xyto resins can also be used for mold construction in the foundry industry. The resulting shaped bodies are commanded by statiains and can be applied by the action of man-o-mani-th-m-z. tv.a-. .. rovat. by the addition of different additives, or if their surface is coated, it is possible to use them in different fields of application.

Examples of the invention

2 "Example 1 * today, consisting of 43 g of commercially available powdered phenolic resin / novolak with hexanetkylentetraminem./ with average grain sizes _of 35 microns and a melting sieving I3O ° C and 3.4 g pigrenovaného powder coating based on a commercial powder epoxy resins as well as 10,22 g.

The pigmented powdered polylaes based lacquer resin, where the powder coating now has a proportion of 13, is homogenized in the mixing agglomerate.

(xolye ' epoxide = 3 " 1.20 parts of powder coating). ¹ ''. ·. The mixture can be stored for a longer period without further loss of reactivity. ,. '' xřík? ad 2,

To 70 g of the phenolic resin analogous to Example 1, a pre-homogenized mixture consisting of 13.8 g of epoxy resin base paint and 14.2 g of powdered epoxy resin are added.

1b of a polyester based lacquer, both powdered lacquers are free of niament.

/ Polyester: ep. rid =: 1.3 parts of powder coating /

To this mixture is added PO g of the flame retardant based on ammonium phosphate, nelaminoborate and aluminum hydroxide and is homogenized using a conventional mixing unit. ^In this case, a slight heating up to 40 [deg.] C. may occur due to the stirring energy, but no sintering of the various components of the mixture should occur.

*

Example j

To 00 g of the phenolic resin of Example 1, PI g of epoxy resin powder pigmented up to 10% barium sulfate was added and homogenized. xotosi.ee admixed > 0.1 g unpented powder; Polyester based lacquer,. as well as 0.4 g of tetrabutylammonium bromide and the entire mixture is then thoroughly homogenized.

[Polyester: epoxy = 1.45% by weight of the powder coating] The mixture is stable for a longer period of storage.

Filter powders from powder coating production are used as polyester powder or epoxy powder. These are homogenized and then an average sample of these proportions is used, for example.

The powders according to Examples 1 to 3 are prepared together with a fiber fleece produced in a known manner which contains more than 10 C 7 ^and cotton fibers. For this purpose, the fibrous webs are mixed MEC -. Anic2 <; / pohyb'ěm E ~ ^_ '^ s homo'm'e'nn'ě ^- powders: alpha binders and passed beats ^-1, my channel / about 2 to 3 min. 3 ° C to 10 ° C). This results in storage-stable prepregs in which α-fiber resins bind together. krepregs can vary depending on the size and content of resin / fiber, the density depends on the intended use between 2p and 75 kg / m \

From these prepregs, shaped bodies are made. and:'. They are formed into the intended shape in the press and cured there for 10 seconds to 110 seconds at temperatures between 140 ° C and 160 ° C. lo cure.uroplasmic / heat heat. firmly stable products. The density can be influenced by the reboiler, optionally by means of a set. pressure .. .Vznikající sesítěué shaped 'body with same can suede - we introduce zoůsobem or vat-FOV can be laminated with * ··. · ^T: -

The shaped bodies thus obtained have an optically homogeneous surface and are shaped. stable a. we eat only a low content of phenol or formaldehyde.

Claims (4)

CLAIMS 1. A composition for the manufacture of molded fibrous web bodies comprising from about 20 to about 45 wt. of a powder blend, containing a t * fr And 30 to 90 rt wt. % phenolic resins aa? / 70 to lu rt wt. powder coating b / 3C to 55 rt wt. % of organic and / or inorganic fibers, characterized in that component a ₂ consists of waste non-crosslinked powder coatings based on reactive groups of epoxy, polyester, polyurethane and / or acrylic resins. A composition according to claim 1, characterized in that it contains further additives and additives. Compound according to one of Claims 1 to 3, characterized in that epoxy resin and polyester resin in a ratio of 1: 0.2 to 1: 7 are used as the powder coating waste. Mixture according to one of Claims 1 to 3, characterized in that: